The present invention relates to novel oxime O-ether compounds and fungicides containing said compound as an active principle for agricultural and horticultural use.
For agricultural and horticultural crop culture, various agricultural plant protection chemicals have been used for controlling plant diseases. However, due to deterioration of plant protection chemicals in their activity and the appearance of resistant stains of plant pathogenic microorganisms to those chemicals, the use of fungicides plant protection use has been restricted. In addition, many fungicides cause phytotoxicity to plants or are toxic to humans and animals. Consequently, although there are many fungicides for plant protection use have been developed and used, most of them are not satisfactory in view of said disadvantages. As a result, there is a need yet to provide fungicides for plant protection use, which do not have the above-described disadvantages and can be used safely.
For example, oxime O-ether compounds similar to the compounds as defined in the present invention are disclosed in EP4754, EP24888, WO93/21157 as compounds having insecticidal and acaricidal activity.
Furthermore, it is disclosed in Jpn. Pat. Appln. Publication (KOKAI) No. 9-3047 that oxime O-ether compounds represent by the following chemical formula are useful as a fungicide. 
It is an object of the present invention to provide novel oxime O-ether compounds, those which can be an excellent fungicide for agricultural and horticultural use, advantageous for the production in an industrial scale, having firm biological effectiveness, and causing less phytotoxicity.
The inventors of the present invention found that the fungicidal activity of said oxime O-ether compounds represented by the following general formula [I] can be enhanced and phytotoxicity caused thereby can be reduced by introducing an oxygen functional group into the 2nd position of the benzene ring of said oxime O-ether compound and a substituent into an arbitrary position, particularly the 6th position of the benzene ring.
Therefore, the present invention is directed to oxime O-ether compounds represented by a general formula [I]; 
wherein
R1 represents C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy, C1-6 alkylthio, amino, mono- or di-(C1-6 alkyl)amino, C1-6 acyloxy, C1-6 alkoxy C1-6 alkyl, C1-6 haloalkyl, hydroxy or Halogen atom;
m represents an integer of 1 to 4, and when m is 2 or more integer, each of R1 may be same or different from one to another;
R2 represents hydrogen atom, C1-6 alkyl or C3-6 cycloalkyl;
R3 and R4 are same or different from one to another and each independently represents hydrogen atom or C1-6 alkyl;
R5 represents hydrogen atom, C1-6 alkyl, C3-6 cycloalkyl, C1-6 haloalkyl, C1-6 alkoxy C1-6 alkyl, C1-6 alkoxy C1-6 alkoxy C1-6 alkyl, C7-10 aralkyl, C7-10 aralkyloxy C1-6 alkyl, C1-6 alkylcarbonyl, C1-6 alkylsulfonyl or C1-6 haloalkylsulfonyl;
R6 represents C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 alkoxy, C1-6 alkoxy C1-6 alkoxy, C1-6 alkylcarbonyloxy, C1-6 alkoxy C1-6 alkyl, C1-6 haloalkyl, cyano, nitro, amino, mono- or di-(C1-6 alkyl)amino, C1-6 alkylcarbonylamino, C1-6 alkylthio, hydroxy or Halogeno atom; and
n represents an integer of 1 to 4, and when n is 2 or more integer, each of R6 may be same or different from one to another, and fungicides for agricultural and horticultural use containing the oxime O-ether compound or a salt thereof as the active ingredient.
More specifically, in the general formula [I],
R1 represents C1-6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers,
an optionally-substituted C3-6 cycloalkyl, such as cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, and 1-methylcyclohexyl,
C1-6 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, and t-butoxy,
C1-6alkylthio, such as methylthio, ethylthio, isopropylthio, and butylthio,
amino,
mono- or di-(C1-6 alkyl)amino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and ethylisopropylamino,
C1-6 acyloxy, such as acetoxy, and propionyloxy, pivaloyloxy,
C1-6 alkoxy C1-6 alkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, and butoxymethyl;
C1-6 haloalkyl, such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl;
hydroxy, or
Halogeno atom atom atom, such as fluorine, chlorine bromine and iodine;
m represents an integer of 1 to 4, and when m is 2 or more integer, each of R1 may be same or different from one another;
R2 represents hydrogen atom,
C1-6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers, or
an optionally-substituted C3-6 cycloalkyl, such as cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexy, and 1-methylcyclohexyl;
R3 and R4 may be same or different from one to another and each independently represents hydrogen atom, or
C1-6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers;
R5 represents hydrogen atom,
C1-6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers,
an optionally-substituted C3-6 cycloalkyl, such as cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, and 1-methylcyclohexyl,
C1-6 haloalkyl, such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl,
C1-6 alkoxy C1-6 alkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, and butoxymethyl,
C1-6 alkoxy C1-6 alkoxy C1-6 alkyl, such as methoxyethoxymethyl and ethoxyethoxymethyl,
C7-10 aralkyl, such as benzyl and phenetyl,
C7-10 aralkyloxy C1-6 alkyl, such as benzyloxymethyl and benzyloxyethyl,
C1-6 alkylcarbonyl, such as acetyl, propionyl, and pivaloyl,
C1-6 alkylsulfonyl, such as methanesulfonyl and ethanesulfonyl, or
C1-6 haloalkylsulfonyl, such as chloromethylsulfonyl and trifluoromethylsulfonyl;
R6 represents C1-6, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers,
an optionally-substituted C3-6 cycloalkyl, such as cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, and 1-methylcyclohexyl,
C2-6 alkenyl, such as vinyl, propenyl, and isopropenyl,
C2-6 alkynyl, such as ethynyl, and propalgyl,
C1-6 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and t-butoxy,
C1-6 alkoxy C1-6 alkoxy, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, propoxymethoxy, and butoxymethoxy,
C1-6 alkylcarbonyl, such as acetoxy, propionyloxy, and pivaloyloxy,
C1-6 alkoxy C1-6 alkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, and butoxymethyl,
C1-6 haloalkyl, such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroehtyl,
cyano, nitro, amino,
mono- or di-(C1-6 alkyl)amino, such as methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and ethylisopropylamino,
C1-6 alyklcarbonylamino, such as acetylamino, and, pivaloylamino,
C1-6 alkylthio, such as methylthio, ethylthio, and isopropylthio,
hydroxy, or
Halogen atom, such as fluorine, chlorine, bromine and iodine; and
n represents an integer of 1 to 4, and when n is 2 or more integer, each of R6 may be same or different from one another.
Of the compounds defined in the present invention, compounds represented by a general formula [Ixe2x80x2]; 
wherein R1, R2, R3, R4, R5, R6, m and n are as defined above, of which benzene ring is substituted by one of the groups exampled above for R6 at the 6th position, have excellent activity as a fungicide for agricultural and horticultural use.
(Fungicide for Agricultural and Horticultural Use)
Each of the compounds defined in the present invention has excellent fungicidal activity against wide range of fungi belonging to, for example, Oomycetes, Ascomycetes, Deuteromycetes and Basidiomycetes. In particular, the compounds of the present invention have remarkable fungicidal activity against a fungus of gray mold disease, Botrytis cinerae, compared to the known compounds described above.
The composition containing the compound of the present invention as the active ingredient can be used for controlling various plant diseases infesting on agricultural and horticultural crops including ornamental flowers, lawns and forage crops by means of seed treatment, foliage application soil application, water surface application, etc.
Example of plant diseases those which can be controlled by the application of a composition containing the compound of the present invention include the following.
Sugar beet: Cercospora leaf spot (Cercospora beticola)
Groundnut: Leaf spot (Mycosphaerella arachidis)
Late leaf spot (Mycosphaerella berkeleyi)
Cucumbers: Powdery mildew (Sphaerotheca fuliginea)
Gummy stem blight (Mycosphaerella melonis)
Sclerotinia rot (Sclerotinia sclerotiorum)
Gray mold (Botrytis cinerea)
Scab (Cladosoorium cucumerinum)
Tomatoes: Gray mold (Botrytis cinerea)
Leaf mold (Cladosporium fulvum)
Eggplants: Gray mold (Botrytis cinerea)
Black rot (Corynespora melongenea)
Powdery mildew (Erysiphe cichoracearum)
Strawberries: Gray mold (Botrytis cinerea) Powdery mildew (Sphaerotheca aphanis)
Onion: Gray-mold neck rot (Botrytis allii)
Gray-mold (Botrytis cinerea)
Kidney bean: Sclerotinia rot (Sclerotinia sclerotiorum)
Gray mold (Botrytis cinerea)
Apples: Powdery mildew (Podosphaera leucotricha)
Scab (Venturia inaequalis)
Blossom blight (Monilinia mali)
Oriental persimon: Powdery mildew (Phyllactinia kakicola)
Anthracnose (Gloeosporium kaki)
Angular leaf spot(Cercospora kaki)
Peach and Cherries: Brown rot (Monilinia fructicola)
Grapes: Gray mold (Botrytis cinerea)
Powdery mildew (Uncinula necator)
Ripe rot (Glomerella cingulata)
Pears: Scab (Venturia nashicola)
Rust (Gymnosporangium asiaticum)
Black spot (Alternaria kikuchiana)
Tea plant: Gray blight(Pestalotia theae)
Anthracnose (Colletotrichum theae-sinensis)
Citrus: Scab (Elsinoe fawcetti)
Blue mold (Penicillium italicum)
Common green mold (Penicillium digitatum)
Gray mold (Botrytis cinerea)
Barley: Powdery mildew (Erysiphe graminis f.sp. hordei)
Loose smut (Ustilago nuda)
Scab (Gibberella zeae)
Leaf rust (Puccinia recondita)
Spot blotch (Cochliobolus sativus)
Eye spot (Pseudocercosporella herpotrichoides)
Glume bltch (Leptosohaeria nodorum)
Powdery mildew (Erysiphe graminis f.sp. tritici)
Snow mould (Micronectriella nivalis)
Paddy rice: Blast (Pyricularia oryzae)
Sheath blight (Rhizoctonia solani)
Bakanae disease (Gibberella fujikuroi)
Helminthosporium leaf spot (Cochliobolus miyabeanus)
Tobacco: Sclerotinia rot (Sclerotinia sclerotiorum)
Powdery mildew (Erysiphe cichoracearum)
Tulip: Garymold (Botrytis cinerea)
Bent grass: Sclerotinia snow blight (Sclerotinia borealis)
Orchard grass: Powdery mildew (Erysiphe graminis)
Soybean: Purple speck (Cercospora kikuchii)
Potatoes and Tomatoes: Downy mildew (Phytophthora infestans)
Cucumbers: Downy mildew (Pseudoperonospora cubensis)
Grape: Downy mildew (Plasmopara viticola)
Besides, in recent years, it should be noted that various plant pathogenic fungi have developed resistance to plant protection chemicals, such as benzimidazole fungicides and carbodiimide fungicides. It follows that there is a problem in the control of such a problematic plant disease, because no fungicide can control those plant diseases sufficiently. Therefore, an effective fungicide, which can control such fungi being resistant against those problematic plant diseases is badly desired. The compounds of the present invention are effective to those resistant strains of fungi to aforementioned fungicides as well as susceptible ones.
The compounds of the present invention are effective to not only the susceptible fungi but also the resistant strains of fungi including gray mold fungus (Botrytis cinerea), sugar beet leaf spot fungus (Cercospora beticola), apple scab fungus (Venturia inaequalis), and pear scab fungus (Venturia nashicola) to, for examples, thiophanate methyl, benomyl and carbendazim.
In addition, the compounds defined in the present invention are also effective against gray mold diseases caused by Botrytis cinerea which are resistant to dicarboxyimide fungicides, such as vinclozolin, procymidone and iprodione. The fungicidal activity against the resistant strains of gray mold fungus of the compounds of the present invention is as effective as that against the susceptible strains.
Specifically, examples of plant diseases to those which a fungicidal composition (fungicide for agricultural and horticultural use) containing the compound of the present invention is used more preferably are Cercospora leaf spot of sugar beet, powdery mildew of wheat, blast of paddy rice, scab of apples, gray mold of Kidney bean, leaf spot of groundnut and so on.
Furthermore, the compounds of the present invention can also be used as an antifouling agent for preventing structures in water, such as the bottoms of ships and fishing nets, from fouling of aqueous life.
The compounds according to the present invention are produced according to a process represent by the following reaction equation; 1) 
wherein R1, R2, R3, R4 and m are as defined above, Ar represents a substituted phenyl group represented by a formula; 
wherein R5, R6 and n are as defined above, and L represents Halogen atom, such as chlorine, bromine and iodine, or an eliminating group, such as methanesulfonyloxy and p-toluenesulfonyloxy.
Specifically, in the reaction equation (1) given above, the compounds represented by the general formula [I] can be produced by allowing a compound of the formula [II] and a compound of the formula [III] to react with each other without solvent or preferably in a solvent while stirring for 10 min. to 24 hours at a reaction temperature of 0 to 150xc2x0 C. and in the presence of a deacidifying agent.
Examples of the solvent to be used in the above reaction (1) include a ketone, such as acetone and 2-butanone, an ether, such as diethyl ether and tetrahydrofuran, an aromatic hydrocarbon, such as benzene and toluene, an alcohol, such as methanol and ethanol, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide and water. One or more solvents recited above can be used in combination for the reaction.
Examples of the base to be used in the above reaction (1) include an inorganic base, such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium hydride, an alkali metal alcolate, such as sodium methylate and sodium ethylate, and an organic base, such as pyridine, triethylamine and DBU.
The stating material represented by the formula [II] for producing the compounds according to the present invention can be produced according to the process disclosed in Jap. Pat. Appln. KOKAI Publication No. 9-3047. 2) 
wherein R1, R2, R3, R4, Ar and m are as defined above.
Specifically, in the reaction equation (2) given above, the compound represented by the general formula [I] is produced by allowing a compound resented by the formula [IV] and a compound represented by the formula [V] or a salt thereof to react with each other while stirring without solvent or preferably in a solvent for a period of from 10 min. to 24 hours at a reaction temperature in a range of from 0 to 150xc2x0 C.
Example of the solvent to be used in the above reaction (2) include an alcohol, such as ethanol and methanol, an ether, such as diethyl ether, tetrahydrofuran and dioxane, a cellosolve, such as methyl cellosolve and ethyl cellosolve, an aromatic hydrocarbon, such as benzene and toluene, acetic acid, N,N-dimethylformamide, dimethylsulfoxide, and water. One or more solvents recited above can also be used in combination for the reaction (2). The reaction (2) does not require the presence of a catalyst, however, the reaction may be accelerated by an addition of an acid or a base sometime. Examples of the catalytic acid include an inorganic acid, such as sulfuric acid and hydrochloric acid, and an organic acid, such as p-toluene sulfonic acid. Examples of the catalytic base include acetic acid and the like.
Following to the completion of the reactions (1) and (2), the targeted compounds can be obtained by subjecting the reaction products to common post-reaction processing. Note that the obtained targeted compounds can be further chemically modified to produce various derivatives thereof. More specifically, as said chemical modification, functional group conversion represented by induction of nitro group to amino group by reduction reaction, deblocking of functional groups, such as methoxymethyl group, recognized in the organic chemistry field as a protecting group, induction of functional groups, such as hydroxy group and amino group, generated by the deblocking by means of alkylation and acylation, and induction of functional groups, represented by Sonogashira reaction, recognized as a deblocking group in the organic chemistry field, such halogenatoms, with use of a nucleophilic reagent are exemplified.
Said salts of the compound of the formula [I] can be produced by performing a reaction of the compound of the formula [I] and either an inorganic acid or an organic acid in an appropriate solvent.
The chemical structures of the compounds according to the present invention are determined by use of NMR, mass spectrum, and so on.
[Fungicide]
The fungicide according to the present invention contains one or more of the compounds defined in the present invention as the active ingredient. In the practical application of the compounds of the present invention, the compounds can be used in a form of the pure compound without combining other component thereto. As well, the compound of the present invention can be prepared in a common formulation form to be used for the purpose of an plant protection chemical, for example, wettable powder, granules, powder, emulsifiable concentrate, water-soluble formulation, suspension concentrate, flowable and so on.
Examples of additives and carriers to be used in the formulations for plant protection use of the compound of the present invention are as follows. For the solid type formulations, phytogenic powdery materials, such as soybean powder and flours, mineral fine powders, such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, and organic and inorganic compounds, such as sodium benzoate, urea and Glauber""s salt.
In case that the compounds of the present invention are prepared to liquid type formulations, petroleum fractions including kerosine, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohols, acetone, trichloroethylene, methyl isobutyl ketone, mineral oils, vegetable oils, water, etc. can be used as a solvent.
In addition, in order to provide uniformity and stability to the exampled formulations, it is possible to add surface active agents into each of the formulations upon necessity. Examples of the surface active agent that can be added to said formulations include a nonionic surface active agent, such as polyoxyethylene-added alkyl phenyl ether, polyoxyethylene-added higher fatty acid ester, polyoxyethylene-added sorbitan higher fatty acid ester and polyoxyethylene-added tristyryl phenyl ether, a sulfate ester of polyoxyethylene-added alkyl phenyl ether, an alkyl benzene sulfonate, a sulfate ester of higher alcohol, an alkyl naphthalene sulfonate, a polycarbonate, a lignin sulfonate, a formaldehyde condensate of alkyl naphthalene sulfonate, and a copolymer of isobutylene-maleic anhydride.
In general, the content of an active ingredient in each of the formulations recited above is preferably in a range of from 0.01 to 90% by weight, and more preferably from 0.05 to 85% by weight based on the total weight of the composition (formulation).
Each of the prepared formulations, such as wettable powder, emulsifiable concentrate and flowable concentrate, is diluted with water so as to prepare the diluted solution or the suspension at a desired concentration and is applied to crop plants by, for example, spraying. For the formulations, such as granular and power formulations, the formulation itself is directly applied to the target crop plants. Therefore, the fungicidal composition according to the present invention prepared into the respective formulation types described above is applied to crop plants, seeds, water surface and soil either directly or in a form of diluted solution with water.
Explanation will now be made for the application dose of the respective formulations. The application dose may differ depending on various conditions, such as climatic condition, a type of formulation, the time of application, an application method, whereto apply, the target disease to be controlled, the target crop plant, etc. However, the application dose based on the active ingredient per hectare is normally in a range of from 1 to 1,000 g, and preferably from 10 to 100 g per hectare.
More specifically, where wettable powder, emulsifiable concentrate, suspension concentrate or liquid formulation is applied by dilution with water, the concentration of the active ingredient in the dilution will be in a range of from 1 to 1,000 ppm, and preferably from 10 to 250 ppm. On the other hand, in case of granular and powder formulations, they are directly applied without making the dilution.
Needless to say that the compound alone according to the present invention has sufficient fungicidal activity, however, it can be combined for the use with one or more of various types of other plant protection chemicals, for example, fungicides, insecticides, acaricides and synergists.
Hereunder, representative examples for fungicides, insecticides, acaricides, nematicides and plant growth regulators those which can be combined to use with the fungicidal composition according to the present invention will be recited.
Fungicides
Copper-base fungicides: Basic copper chloride, Basic copper sulfate, etc.
Sulfur-base fungicides: Thiuram, Zineb, Maneb, Mancozeb, Ziram, Propineb, Polycarbamate, etc.
Polyhaloalkylthio-type fungicides: Captan, Folpet, Dichlorfluanid, etc.
Organochloric fungicides: Chlorothalonil, Fthalide, etc.
Organophosphorous fungicides: IBP, EDDP, Triclofos methyl, Pyrazophos, Fosetyl, etc.
Benzimidazol fungicides: Thiophanate methyl, Benomyl, Carbandazim, Thiabendazol, etc.
Dicarboxyimide fungicides: Iprodione, Procymidone, Vinclozolin, Fluorimide, etc.
Carboxyamide fungicides: Oxycarboxine, Mepronil, Flutolanil, Tecloftalam, Trichlamide, Pencycuron, etc.
Acylalanine fungicides: Metalaxyl, Oxadixyl, Fralaxyl, etc.
Methoxyacrylate fungicides: Clethoxime methyl, Azoxystrobine, Methominostrobine, etc.
Anilinopyrimidine fungicides: Andopurine, Mepaniprim, Pyrimethanil, Diprodinyl, etc.
SBI fungicides: Triadimefon, Triadimenol, Bitertanol, Microbutanil, Hexaconazol, Propiconazol, Triflumizole, Prochloraz, Beflazoate, Fenarimol, Pyrifenox, Triforine, Flusilazole, Etaconazole, Dicloputrazole, Fluotrimazole, Flutriafen, Penconazole, Diniconazole, Imazalyl, Tridemorph, Fenpropimorph, Buthiobate, Epoxyconazole, Metoconazole, etc.
Antibiotics: Polyoxins, Blastocidin-S, Kasugamycin, Balidamycin, Dihydrostreptomycin sulfate, etc.
Others: Propamocarbhydrochloride, Quintozene, Hydroxyisoxazole, Metasulfocarb, Anilazine, Isoprothiolane, Probenazole, Quinomethionate, Dithianone, Dinocap, Diclomezine, Ferimzone, Fluazinam, Pyroquilon, Tricyclazole, Oxilinic acid, Dithianone, Iminoctadine acetate, Cymoxanil, Pyrrolenitrine, Metasulfocarb, Diethofencarb, Binapacryl, Lecithin, Sodium hydrogen atomcarbonate, Fenaminosulf, Dodine, Dimetomorph, Fenazine oxide, Carpropamide, Flusulfamide, Fludioxonil, Famoxidone, etc.
Insecticides and Acaricides
Organophosphorous and carbamate insecticides: Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Bamidothion, Fenthoate, Dimethoate, Formothion, Malathon, Trochlorfon, Thiometon, Phosmet, Dichlorvos, Acephate, EPBP, Methyl parathion, Oxadimeton methyl, Ethion, Salithion, Cyanophos, Isoxathione, Pyridafenthion, Phosalone, Methidathion, Sulprofos, Chlorfevinphos, Tetrachlorvinphos, Dimethylvinphos, Propaphos, Isofenphos, Ethyl thimeton, Profenophos, Pyraclofos, Monocrotophos, Azinphosmethyl, Aldicarb, Methomyl, Dithicarb, Carbofuran, Carbosulfan, Benflacarb, Flathiocarb, Propoxur, BPMC, MTMC, MIPC, carbaryl, Pyrimicarb, Rthifencarb, Fenoxycarb, etc.
Pyrethroid insecticides: Permethrin, Cypermethrin, Deltamethrin, Fenvalerate, Fenpropathrin, Pyrethrin, Allethrin, Tetramethrin, Resmethrin, Dimethrin, Propathrin, Fenothrin, Prothrin, Fluvarinate, Cyfluthrin, Cyhalothrin, Flucythrinate, Ethofenprox, Cycloprothrin, Tralimethrin, Silafluofen, Profenprox, Acrinathrin, etc.
Bezoyl urea and other insecticides: Diflubenzuron, Chlorfluazuron, Hexaflumuron, Triflumuron, Tetrabenzuron, Fulfenoxuron, Flucycloxuron, Buprofezin, Pyriproxyfen, Methoprene, Benzoepin, Diafenthiuron, Acetamiprid, Imidacloprid, Nitenpyram, Fipronyl, Cartap, Thiocyclam, Bensultap, Nicotin sulfate, Rotenone, Metaldehyde, Machine oil, Microbial insecticides such as BT and insect-pathogenic viruses, etc.
Nematicides: Fenamiphos, Fosthiazate, etc.
Acaricides
Chlorbenzilate, Fenisobromolate, Dicofol, Amitraz, BPPS, Benzomate, Hexythiazox, Fenbutatin oxide, Polynactin, Quinomethionate, CPCBS, Tetradifon, Avermectin, Milbemectin, Clofentezin, Cyhexatin, Pyridaben, Fehproxymate, Tebufenpyrad, Pyrimidifen, Fenothiocarb, Dienochlor, etc.
Plant Growth Regulators: Gibberellin s(e.g., Gibberellin A3, Gibberellin A$, Gibberellin A7), IAA, NAA, etc.